Photodissociation cross section of ClOOCl at 330 nm.

The photolysis rate of ClOOCl is crucial in the catalytic destruction of polar stratospheric ozone. In this work, we determined the photodissociation cross section of ClOOCl at 330 nm with a molecular beam and with mass-resolved detection. The photodissociation cross section is the product of the absorption cross section and the dissociation quantum yield. We formed an effusive molecular beam of ClOOCl at a nozzle temperature of 200 or 250 K and determined its photodissociation probability by measuring the decrease of the ClOOCl intensity upon laser irradiation. By comparing with a reference molecule (Cl(2)), of which the absorption cross section and dissociation quantum yield are well-known, we determined the absolute photodissociation cross section of ClOOCl at 330 nm to be (2.31 +/- 0.11) x 10(-19) cm(2) at 200 K and (2.47 +/- 0.12) x 10(-19) cm(2) at 250 K. Impurity interference has been a well-recognized problem in conventional spectroscopic studies of ClOOCl; our mass-resolved measurement directly overcomes such a problem. This measurement of the ClOOCl photolysis cross section at 330 nm is particularly useful in constraining its atmospheric photolysis rate, which in the polar stratosphere peaks near this wavelength.